JP6158312B2 - Method for obtaining carboxymethylcellulose from agricultural industrial residues, carboxymethylcellulose and use thereof - Google Patents
Method for obtaining carboxymethylcellulose from agricultural industrial residues, carboxymethylcellulose and use thereof Download PDFInfo
- Publication number
- JP6158312B2 JP6158312B2 JP2015510581A JP2015510581A JP6158312B2 JP 6158312 B2 JP6158312 B2 JP 6158312B2 JP 2015510581 A JP2015510581 A JP 2015510581A JP 2015510581 A JP2015510581 A JP 2015510581A JP 6158312 B2 JP6158312 B2 JP 6158312B2
- Authority
- JP
- Japan
- Prior art keywords
- carboxymethylcellulose
- solution
- sodium
- cmc
- isopropanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 229920002134 Carboxymethyl cellulose Polymers 0.000 title claims description 73
- 239000001768 carboxy methyl cellulose Substances 0.000 title claims description 73
- 235000010948 carboxy methyl cellulose Nutrition 0.000 title claims description 71
- 239000008112 carboxymethyl-cellulose Substances 0.000 title claims description 71
- 238000000034 method Methods 0.000 title claims description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000011230 binding agent Substances 0.000 claims description 34
- 239000000835 fiber Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 17
- 244000060011 Cocos nucifera Species 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- -1 filtering Chemical compound 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 238000004061 bleaching Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000004537 pulping Methods 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000008188 pellet Substances 0.000 claims description 7
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 229960002218 sodium chlorite Drugs 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 235000013305 food Nutrition 0.000 claims description 4
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 235000013373 food additive Nutrition 0.000 claims 1
- 239000002778 food additive Substances 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 239000000825 pharmaceutical preparation Substances 0.000 claims 1
- 229940127557 pharmaceutical product Drugs 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 11
- 229920002678 cellulose Polymers 0.000 description 9
- 239000001913 cellulose Substances 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 238000005453 pelletization Methods 0.000 description 9
- 238000002329 infrared spectrum Methods 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920003043 Cellulose fiber Polymers 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000006072 paste Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229920000881 Modified starch Polymers 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 235000019426 modified starch Nutrition 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 235000020415 coconut juice Nutrition 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000000774 hypoallergenic effect Effects 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000008141 laxative Substances 0.000 description 1
- 229940125722 laxative agent Drugs 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000021962 pH elevation Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
- A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
- A23L29/262—Cellulose; Derivatives thereof, e.g. ethers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
- A61K9/16—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction
- A61K9/1605—Excipients; Inactive ingredients
- A61K9/1629—Organic macromolecular compounds
- A61K9/1652—Polysaccharides, e.g. alginate, cellulose derivatives; Cyclodextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/06—Rendering cellulose suitable for etherification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
- C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
- C08L1/28—Alkyl ethers
- C08L1/286—Alkyl ethers substituted with acid radicals, e.g. carboxymethyl cellulose [CMC]
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/20—Chemically or biochemically modified fibres
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/25—Cellulose
- D21H17/26—Ethers thereof
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Description
本願は、ここにその全文を参考文献として含める「農業関連産業残留物に由来する天然繊維を基材とするバインダー、および天然繊維を基材とするバインダーを得る方法」と題する米国特許出願公開第61/644,856号、2012年5月9日提出、の優先権を主張する。 This application is hereby incorporated by reference in its entirety, U.S. Patent Application Publication entitled “Natural Fiber-Based Binders Derived from Agricultural Industrial Residues, and Methods for Obtaining Natural Fiber-Based Binders”. Claims priority of 61 / 644,856, filed May 9, 2012.
発明の分野
本発明は、農業関連産業残留物に由来する繊維を基材とするバインダーを得る方法、および前記方法により製造されたカルボキシメチルセルロースに関するものである。
FIELD OF THE INVENTION The present invention relates to a method for obtaining a fiber-based binder derived from agricultural-related industrial residues and to carboxymethylcellulose produced by said method.
関連技術の説明
ナトリウムカルボキシメチルセルロース(CMC)で製造されたバインダーの幾つかは、技術的に公知である。以下に、そのようなバインダーおよびそれらの対応する製造方法の例を示す。
2. Description of Related Art Some of the binders made with sodium carboxymethylcellulose (CMC) are known in the art. The following are examples of such binders and their corresponding production methods.
ブラジル国特許第PI0,801,555−4号には、鉄鉱石をペレット化するためのバインダーが記載されている。このバインダーは、細かく粉砕した鉄鉱石の結合に使用する、ベントナイトおよび多糖を含む。この発明は、また、バインダーとして多糖およびベントナイトを含んでなる組成物を使用する、鉄鉱石のペレットを提供する方法に関するものである。 Brazilian Patent No. PI 0,801,555-4 describes a binder for pelletizing iron ore. This binder contains bentonite and polysaccharides used to bind finely ground iron ores. The invention also relates to a method for providing iron ore pellets using a composition comprising polysaccharide and bentonite as binders.
米国特許第4,410,694号には、反応容器に詰めたセルロース繊維を通して、均質なアルカリ性反応液を、該セルロース繊維1kgあたり10L/分を超える該反応液の流量で、該セルロース繊維をカルボキシメチルセルロース繊維に実質的に完全に転化させるのに十分な時間連続的に循環させることを含んでなる、カルボキシメチルセルロース繊維の製造方法が記載されており、そのセルロース繊維は、天然セルロース繊維および再生セルロース繊維からなる群から選択され、該反応液は、有効量の、モノクロロ酢酸およびその塩からなる群から選択されたエーテル化剤を含んでなり、そのエーテル化剤は、実質的にエタノールおよび水からなる均質なアルカリ性溶剤に溶解している。 In U.S. Pat. No. 4,410,694, a homogeneous alkaline reaction liquid is passed through cellulose fibers packed in a reaction vessel, and the cellulose fibers are carboxylated at a flow rate of the reaction liquid exceeding 10 L / min. A process for the production of carboxymethylcellulose fibers is described, comprising continuously circulating for a time sufficient for substantially complete conversion to methylcellulose fibers, said cellulose fibers comprising natural and regenerated cellulose fibers And the reaction solution comprises an effective amount of an etherifying agent selected from the group consisting of monochloroacetic acid and salts thereof, the etherifying agent consisting essentially of ethanol and water. Dissolved in a homogeneous alkaline solvent.
米国特許第3,900,463号には、置換度の一様な分布を有するアルカリカルボキシメチルセルロースの製造方法であって、アルカリモノクロロアセテートおよび低級アルキルモノクロロアセテートからなる群から選択されたエーテル化剤でセルロースを、少なくとも一種の有機溶剤および水からなる溶剤系の存在下で、セルロース中にエーテル化剤が一様に分布するまで処理し、エーテル化剤は、無水セルロースグルコース単位1個あたり0.4〜2.0モルで使用され、得られた混合物にアルカリを加え、アルカリは、アルカリモノクロロアセテートに対して等モル以上又は低級アルキルモノクロロアセテートに対して2倍モル以上の量で使用され、続いて室温から環流温度までの温度でエーテル化が完了するまで処理する、方法が記載されている。 U.S. Pat. No. 3,900,463 discloses a process for producing alkali carboxymethyl cellulose having a uniform distribution of substitution degree, comprising an etherifying agent selected from the group consisting of alkali monochloroacetate and lower alkyl monochloroacetate. Cellulose is treated in the presence of a solvent system consisting of at least one organic solvent and water until the etherifying agent is uniformly distributed in the cellulose, the etherifying agent being 0.4 per anhydrocellulose glucose unit. Alkaline is used in an amount of at least equimolar with respect to the alkali monochloroacetate or more than twice the mole with respect to the lower alkyl monochloroacetate, followed by addition of alkali to the resulting mixture. The process is carried out at a temperature from room temperature to reflux temperature until etherification is complete. It has been mounting.
米国特許第4,401,813号には、塩化カルシウム水溶液中で優れたレオロジーおよび流体損失特性を示すカルボキシメチルセルロースの製造方法が記載されており、該方法は、酸素の非存在下で、350℃未満の温度で、86.9±2重量%イソプロパノールを含む水溶液中で、イソプロパノール−水溶液とセルロースの重量比2:1〜7.5:1で、その後に続くアルカリセルロースのエーテル化の際の水酸化アルカリ金属とモノクロロ酢酸のモル比が2.00:1より大きくなるような十分な水酸化アルカリ金属の存在下で、高分子量セルロースの導電性苛性化を行うことを含んでなり、使用するモノクロロ酢酸が約2重量%未満のジクロロ酢酸を含む。 U.S. Pat. No. 4,401,813 describes a process for the production of carboxymethylcellulose which exhibits excellent rheological and fluid loss properties in aqueous calcium chloride solution, which is 350 ° C. in the absence of oxygen. In an aqueous solution containing 86.9 ± 2% by weight isopropanol at a temperature of less than 1% by weight of isopropanol-water solution to cellulose in a ratio of 2: 1 to 7.5: 1, followed by water during the etherification of the alkali cellulose. Comprising conducting a causticization of the high molecular weight cellulose in the presence of sufficient alkali metal hydroxide such that the molar ratio of alkali metal oxide to monochloroacetic acid is greater than 2.00: 1. Acetic acid contains less than about 2% by weight of dichloroacetic acid.
鉱業で使用される、より具体的には鉱石のバインダーとして使用される、CMCは、鉱石粒子を凝集させる役割がある。ペレット形成は、ペレット化工程の最も重要な段階の一つであり、幾つかのファクターにより影響され、最終製品の品質に直接関わる。 CMC, used in the mining industry, more specifically as an ore binder, has the role of agglomerating ore particles. Pellet formation is one of the most important stages of the pelletization process, is affected by several factors and directly affects the quality of the final product.
加国特許第1,336,641号には、10%〜90%の水溶性ナトリウムカルボキシメチルセルロースおよび10%〜90%の炭酸ナトリウムを含む、水の存在下における鉄鉱石用バインダーが記載されている。この特許は、鉱石中におけるバインダーの使用方法も記載している。 Canadian Patent 1,336,641 describes a binder for iron ore in the presence of water comprising 10% to 90% water-soluble sodium carboxymethyl cellulose and 10% to 90% sodium carbonate. . This patent also describes how to use the binder in the ore.
加国特許第1,247,306号には、水の存在下でヒドロキシエチルセルロースおよび炭酸ナトリウムからなるバインダーを使用する、鉄鉱石粒子の結合方法が記載されている。 Canadian Patent 1,247,306 describes a method for binding iron ore particles using a binder consisting of hydroxyethyl cellulose and sodium carbonate in the presence of water.
米国特許第4,288,245号には、アルカリ金属塩およびカルボキシメチルセルロースを少なくとも0.01%の量で、アルカリ金属および酸に由来する一種以上の塩との組合せで含むペーストの存在下における、金属鉱石のペレット化方法が記載されている。 US Pat. No. 4,288,245 describes the presence of a paste comprising an alkali metal salt and carboxymethyl cellulose in an amount of at least 0.01% in combination with one or more salts derived from alkali metal and acid, A method for pelletizing metal ore is described.
米国特許第4,486,335号には、鉄を含む鉱石のバインダーを製造する方法およびその方法の製品が記載されている。この発明は、カルボキシメチルヒドロキシエチルセルロースを基剤とするバインダーを記載しているが、このバインダーは、水溶液中のアルミニウムイオンに結合した時に、ゲルを形成する。 U.S. Pat. No. 4,486,335 describes a process for producing iron-containing ore binders and products of the process. The present invention describes a binder based on carboxymethylhydroxyethyl cellulose, which forms a gel when bound to aluminum ions in an aqueous solution.
米国特許第4,597,797号には、水の存在下における鉱石のバインダーおよびバインダーとしてカルボキシメチルセルロースのアルカリ金属塩が記載されている。この組成物は、カルボキシメチルセルロースのアルカリ金属塩およびアルカリ金属および弱酸に由来する一種以上の塩を含んでなる。弱酸のアルカリ塩は、好ましくは酢酸、安息香酸、乳酸、プロピオン酸、酒石酸、コハク酸、クエン酸、亜硝酸、ホウ酸および炭酸に由来する。 U.S. Pat. No. 4,597,797 describes an ore binder in the presence of water and an alkali metal salt of carboxymethyl cellulose as a binder. The composition comprises an alkali metal salt of carboxymethylcellulose and one or more salts derived from alkali metals and weak acids. The alkali salts of weak acids are preferably derived from acetic acid, benzoic acid, lactic acid, propionic acid, tartaric acid, succinic acid, citric acid, nitrous acid, boric acid and carbonic acid.
米国特許第4,863,512号は、水の存在下における濃縮された鉱石材料を結合するのに有用な、カルボキシメチルセルロースのアルカリ金属塩およびトリポリリン酸ナトリウムを含んでなるバインダー、濃縮された鉱石材料をそのようなペーストで結合する方法、およびそのような方法から得られる結合された製品に関する。 U.S. Pat. No. 4,863,512 discloses a binder comprising an alkali metal salt of carboxymethyl cellulose and sodium tripolyphosphate, a concentrated ore material useful for binding the concentrated ore material in the presence of water. Relates to a method of bonding with a paste, and to a bonded product obtained from such a method.
米国特許第4,919,711号には、水の存在下で濃縮された鉱石材料を結合させるのに有用な、カルボキシメチルセルロース又はカルボキシメチルヒドロキシエチルセルロースのアルカリ金属塩およびトリポリリン酸ナトリウムから選択された水溶性重合体を含んでなる、バインダーが開示されている。この生成物に加えて、この特許は、濃縮された鉱石材料をそのようなペーストで結合させる方法、およびそのような方法から得られる結合された製品を記載している。 U.S. Pat. No. 4,919,711 discloses an aqueous solution selected from carboxymethylcellulose or alkali metal salts of carboxymethylhydroxyethylcellulose and sodium tripolyphosphate, useful for binding concentrated ore materials in the presence of water. Binders comprising a functional polymer are disclosed. In addition to this product, this patent describes a method of combining concentrated ore material with such a paste, and a combined product resulting from such a method.
米国特許第6,497,746号は、粒子を結合する(例えばペレット化する)ための方法、およびそのような方法により製造された製品(即ちペレット)を記載している。これは粒子状材料を結合する方法であり、有効量の濡らすための水、結合するのに有効量のデンプン、変性デンプン、デンプン誘導体、アルギン酸塩、ペクチンおよびそれらの混合物から選択された重合体、および結合するのに有効な量の、混合物を製造するための弱酸の塩を含んでなる。 U.S. Pat. No. 6,497,746 describes a method for binding (eg, pelletizing) particles and products produced by such a method (ie, pellets). This is a method of binding particulate material, a polymer selected from an effective amount of water for wetting, an effective amount of starch to bind, modified starch, starch derivatives, alginate, pectin and mixtures thereof; And an effective amount to bind, comprising a salt of a weak acid to produce a mixture.
ブラジルは、農産工業廃棄物の最大発生国の一つである。これらの廃棄物は、前処理を全く行わずに環境中に放出され、幾つかの損害を与えている。 Brazil is one of the largest producers of agricultural industrial waste. These wastes are released into the environment without any pretreatment and cause some damage.
農産工業繊維残留物として、ココナツは、この点で突出しており、大規模生産されている。ブラジルにおけるココナツの年間生産量は、15億ユニットを超え、28ヘクタールを超える面積で収穫されている。ココナツ生産活動の処理は、ココナツ水およびココナツを得るために重要な固体胚乳を取った後の廃棄物であり、繊維状外果皮、中果皮および内果皮によって代表される残りの部分は、果実の成分の約45%を構成する。そのような残留物は、廃棄するのが困難であり、ゴミ捨て場や埋め立て地に送られ、これらの場所に輸送するために工業コストを増加させる。 As an agro-industrial fiber residue, coconut stands out in this respect and is produced on a large scale. The annual production of coconuts in Brazil exceeds 1.5 billion units and is harvested over 28 hectares. The treatment of coconut production activity is waste after taking coconut water and solid endosperm important to obtain coconut, and the rest represented by fibrous outer pericarp, mesocarp and inner pericarp It constitutes about 45% of the ingredients. Such residues are difficult to dispose of and are sent to garbage dumps and landfills, increasing industrial costs for transport to these locations.
上記の問題に対して、本発明は、農産工業廃棄物を使用してカルボキシメチルセルロースを得るための、持続可能な代替方法に関するものである。 In response to the above problems, the present invention relates to a sustainable alternative method for obtaining carboxymethylcellulose using agricultural industrial waste.
本発明により提案される方法により、およそ200万トンにもなるココナツ繊維中果皮の、膨大な量の上記廃棄物を、カルボキシメチルセルロースの製造用原料として使用することができる。 According to the method proposed by the present invention, an enormous amount of the above waste of coconut fiber mesocarp which is about 2 million tons can be used as a raw material for producing carboxymethyl cellulose.
発明の概要
上記の問題およびまだ対処されていないニーズに鑑みて、本発明は、農産工業残留物からカルボキシメチルセルロース(CMC)を得るための有利で効果的な方法であって、a)原料が、洗浄され、乾燥され、粉砕され、再度洗浄される、原料を準備する工程、b)工程a)から得られた生成物を水酸化ナトリウムと反応させるパルプ化工程、c)パルプを粉砕すること、イソプロパノールおよび蒸留水の溶液を、室温で撹拌しながら加えること、NaOH水溶液を混合物がアルカリ化するまで加えること、イソプロパノール中のモノクロロ酢酸を加えること、濾過すること、メタノール溶液中に懸濁させること、および酢酸で中和させることからなる合成工程を含んでなる、方法を記載するものである。
SUMMARY OF THE INVENTION In view of the above problems and unmet needs, the present invention is an advantageous and effective method for obtaining carboxymethylcellulose (CMC) from agro-industrial residues, wherein a) Washing, drying, crushing, washing again, preparing the raw material, b) a pulping step in which the product obtained from step a) is reacted with sodium hydroxide, c) crushing the pulp, Adding a solution of isopropanol and distilled water with stirring at room temperature, adding aqueous NaOH until the mixture is alkalized, adding monochloroacetic acid in isopropanol, filtering, suspending in methanol solution, And a process comprising a synthesis step comprising neutralizing with acetic acid.
本発明は、また、幾つかの工業的方法に使用されうる前記方法から得られたCMCに関するものである。 The invention also relates to a CMC obtained from said process that can be used in several industrial processes.
本発明によるこれら態様のさらなる優位性および新規な特徴は、下記の説明に一部記載され、一部は、後述の実施例により、又は本発明を実践することにより、当業者にはより明らかになる。 Additional advantages and novel features of these aspects according to the present invention will be set forth in part in the description which follows, and in part will become more apparent to those skilled in the art by the following examples or by practicing the invention. Become.
図面の簡単な説明
システムおよび方法の様々な例態様を、以下の図面を参照しながら詳細に説明するが、これらに限定されない。
発明の詳細な説明
以下の詳細な記述は、本発明の範囲、応用性又は形態を一切制限するものではない。より正確には、以下の記述は、代表的な態様を実行するために必要な理解を与えるものである。ここで与えられる開示を使用する時、当業者は、本発明の範囲を推定することなく、使用できる好適な代替案を理解することができる。
DETAILED DESCRIPTION OF THE INVENTION The following detailed description does not in any way limit the scope, applicability, or form of the invention. More precisely, the following description gives the understanding necessary to carry out representative aspects. When using the disclosure provided herein, one of ordinary skill in the art will appreciate suitable alternatives that may be used without extrapolating the scope of the invention.
本発明は、農業関連産業残留物に由来する天然CMC成分を得るための方法、より具体的にはココナツ繊維に由来する天然CMCを得るための方法、に関するものである。 The present invention relates to a method for obtaining natural CMC components derived from agricultural-related industrial residues, more specifically a method for obtaining natural CMC derived from coconut fibers.
さらに具体的には、本発明は、天然CMC成分を得るための方法であって、以下の工程、すなわち
a)原料を準備すること、
b)パルプ化工程、
c)CMCの合成
を含んでなるものである。
More specifically, the present invention is a method for obtaining a natural CMC component comprising the following steps: a) preparing a raw material,
b) pulping process,
c) comprising the synthesis of CMC.
工程a)では、農産工業繊維残留物、例えばココナツ繊維、を水で洗浄し、大まかな不純物を除去する。そのような洗浄の後、繊維を、炉中、30〜120℃で4〜72時間乾燥させる。 In step a), agro-industrial fiber residues, such as coconut fibers, are washed with water to remove rough impurities. After such washing, the fibers are dried in an oven at 30-120 ° C. for 4-72 hours.
繊維を粉砕機で粉砕し、18〜140メッシュ(1.00〜0.105mm)の篩を通して篩分ける。 The fiber is pulverized with a pulverizer and sieved through a 18-140 mesh (1.00-0.105 mm) sieve.
粉砕された後、生成物は蒸留水で洗浄され、次いで濾過される。沈殿物を炉中30〜120℃で4〜72時間乾燥させる。 After being ground, the product is washed with distilled water and then filtered. The precipitate is dried in an oven at 30-120 ° C. for 4-72 hours.
得られた生成物からリグニンを除去するために、工程b)(パルプ化工程)では、工程a)で得られた、粉砕され、洗浄された繊維の塊を、水酸化ナトリウム5〜25%(m/v)と1:10の比で10〜100分間混合し、撹拌しながら反応させる。 In order to remove lignin from the product obtained, in step b) (pulping step), the ground and washed fiber mass obtained in step a) is mixed with 5 to 25% sodium hydroxide ( m / v) at a ratio of 1:10 for 10 to 100 minutes and allowed to react with stirring.
所望により、反応混合物を撹拌した後、圧力0.5〜3.0Kgf/cm2を、10〜100分間、温度111〜143℃で加えることができる。 Optionally, after stirring the reaction mixture, a pressure of 0.5-3.0 Kgf / cm 2 can be added at a temperature of 111-143 ° C. for 10-100 minutes.
反応混合物を中性pHで水洗し、その沈殿物を炉中、約12〜18時間、30〜120℃で処理する。 The reaction mixture is washed with water at neutral pH and the precipitate is treated in an oven at 30-120 ° C. for about 12-18 hours.
工程b)から得られた生成物は、CMC合成(工程c)のために制御された撹拌および温度によって処理される。最初に、乾燥させたパルプが粉砕され、次いでイソプロパノール(1:15〜1:30)および蒸留水(1:0.5〜1:3) の溶液が加えられる。この系を、室温で10〜30分間撹拌のもとで保持する。その後、NaOH水溶液25〜55%(w/v)を、1:15の比の乾燥パルプに加える。水酸化ナトリウム溶液を、室温で撹拌しながら、30分間かけて滴下して加え、加えた後、混合物を室温で60分間撹拌する。 The product obtained from step b) is treated with controlled stirring and temperature for CMC synthesis (step c). First, the dried pulp is ground and then a solution of isopropanol (1: 15-1: 30) and distilled water (1: 0.5-1: 3) is added. The system is kept under stirring at room temperature for 10-30 minutes. Thereafter, 25-55% (w / v) aqueous NaOH solution is added to the dried pulp in a ratio of 1:15. Sodium hydroxide solution is added dropwise over 30 minutes with stirring at room temperature, and after addition, the mixture is stirred at room temperature for 60 minutes.
セルロースのアルカリ化の直後、イソプロパノール(1:1〜1:5)にモノクロロ酢酸(1:1.5〜1:3.5)を入れた溶液が加えられる。そのような溶液は、室温で撹拌しながら、10〜40分間かけて滴下して加える。次いで、温度を40〜70℃に上げ、反応を2〜5時間進行させる。 Immediately after the alkalinization of the cellulose, a solution of monochloroacetic acid (1: 1.5-1: 3.5) in isopropanol (1: 1-1: 5) is added. Such a solution is added dropwise over 10-40 minutes with stirring at room temperature. The temperature is then raised to 40-70 ° C. and the reaction is allowed to proceed for 2-5 hours.
合成後、生成物が濾過され、次いで70〜90%メタノール溶液(v/v)中に懸濁され、酢酸で中和され、5〜20分間撹拌される。これが濾過され、60〜90%メタノールで2回、P.A.メタノールで2回洗浄され、最後にCMCは乾燥される。 After synthesis, the product is filtered and then suspended in 70-90% methanol solution (v / v), neutralized with acetic acid and stirred for 5-20 minutes. This was filtered and washed twice with 60-90% methanol. A. Wash twice with methanol and finally dry the CMC.
所望により、パルプ化工程b)の後、材料を漂白することができる。この工程を行うか、否かは、最終結果、すなわち最終材料が漂白されうるか否かによって決まる。 If desired, the material can be bleached after pulping step b). Whether this step is performed or not depends on the final result, i.e. whether the final material can be bleached.
パルプ化工程b)で得られた、蒸留水(1:40の比で)を含む粗製パルプは、撹拌され、温度60℃に維持される。熱平衡に達した後、氷酢酸(1:0.125〜1:1)および亜塩素酸ナトリウム(1:0.5〜1:4)が加えられる。反応混合物は一定撹拌下に0.5〜1.5時間維持され、次いで氷浴中で10℃未満に冷却される。次いで、混合物は、濾液が中性pHで無色になるまで濾過される。その後、室温で90分間撹拌のもとで、水酸化ナトリウム0.1mol/Lの溶液で分離が行われるその後、そのパルプは再度濾過され、炉液が中性pHに達するまで蒸留水で洗浄される。 The crude pulp obtained in pulping step b) containing distilled water (in a ratio of 1:40) is stirred and maintained at a temperature of 60 ° C. After reaching thermal equilibrium, glacial acetic acid (1: 0.125-1: 1) and sodium chlorite (1: 0.5-1: 4) are added. The reaction mixture is maintained for 0.5 to 1.5 hours under constant stirring and then cooled to below 10 ° C. in an ice bath. The mixture is then filtered until the filtrate is colorless at neutral pH. Thereafter, separation is carried out with a solution of sodium hydroxide 0.1 mol / L under stirring for 90 minutes at room temperature. Thereafter, the pulp is filtered again and washed with distilled water until the furnace liquid reaches a neutral pH. The
本発明のカルボキシメチルセルロースを得る方法により、公知技術より穏やかなアルカリ処理(パルプ化)を使用して、約80%のリグニンを農産工業残留物から除去することができ、初期工程における節約となる。 By the method of obtaining carboxymethylcellulose of the present invention, about 80% of lignin can be removed from agricultural industrial residues using a milder alkali treatment (pulping) than known techniques, resulting in savings in the initial process.
さらに、本発明の所望により行う化学的漂白工程により、ポリフェノール95〜100%除去を達成することができ、その工程の際、反応時間の調整および環流の使用が、高品質の製品を得るのに極めて重要であることが明らかになった。 Furthermore, the optional chemical bleaching step of the present invention can achieve 95-100% removal of polyphenols, during which time adjustment of the reaction time and use of reflux can result in a high quality product. It became clear that it was extremely important.
得られた天然CMCは、幾つかの工業の工程に使用できる。得られた天然CMCは、鉱業で、天然繊維基材のバインダーとして使用でき、その天然繊維基材のバインダーは、材料の混合物を含んでなり、最終製品のバインダーとして優位性を発揮する。 The resulting natural CMC can be used in several industrial processes. The resulting natural CMC can be used as a binder for natural fiber bases in the mining industry, and the natural fiber base binder comprises a mixture of materials and exhibits superiority as a binder in the final product.
例えば、鉱石粒子を結合するには、バインダー組成物は、種類、供給源および鉱石組成により、様々である。 For example, to bind ore particles, the binder composition varies depending on the type, source and ore composition.
これらの成分は、以下となりうる。
−農産工業繊維残留物からのCMC40〜65%、
−炭酸ナトリウム15〜40%、
−亜塩素酸ナトリウム5〜30%、
−その他0〜20%、これはクエン酸ナトリウム、ナトリウムグルコラートおよび水酸化ナトリウム等である。水酸化ナトリウムは、ペレット化方法における活性化および効率増加にも使用されうる。
These components can be:
-CMC 40-65% from agricultural industrial fiber residue,
-15-40% sodium carbonate,
-Sodium chlorite 5-30%,
Other 0-20%, such as sodium citrate, sodium gluconate and sodium hydroxide. Sodium hydroxide can also be used for activation and increased efficiency in the pelletization process.
これらの成分の混合物は、固体−固体混合物又は固体−液体分散液として存在することができ、どちらの場合も、CMCは固体部分であり、添加物は固体又は液体でよい。 The mixture of these components can exist as a solid-solid mixture or a solid-liquid dispersion, in which case the CMC is a solid part and the additive can be a solid or a liquid.
農産工業繊維残留物に由来する天然繊維を基材とする組成物は、鉱石のバインダーとして使用される場合、鉱石粒子を凝集させる役割を果たす。ペレット形成は、ペレット化工程の最も重要な段階の一つであり、幾つかのファクターにより影響され、最終製品の品質に直接的な結果をもたらす。天然繊維を基材とする組成物の品質は、ペレット形成に最も重要な必要条件の一つであり、好適な特性を確保する。 Compositions based on natural fibers derived from agricultural industrial fiber residues, when used as ore binders, serve to agglomerate ore particles. Pellet formation is one of the most important steps of the pelletizing process and is influenced by several factors, which have a direct consequence on the quality of the final product. The quality of the composition based on natural fibers is one of the most important requirements for pellet formation and ensures suitable properties.
さらに、ここに記載する工程により得られるCMCは、食品工業で、粘度改良剤又は増粘剤として、アイスクリームを包む様々な製品でエマルションを安定化させるのに使用される。また、CMCは、多くの非食品製品、例えばパーソナル潤滑剤、歯磨きペースト、下剤、ダイエットピル、水性塗料、洗剤、織物のり付け、および各種紙製品、の構成物質でもある。CMCは、高い粘度を有し、非毒性であり、低アレルギー性なので、第一に使用される。 Furthermore, the CMC obtained by the process described herein is used in the food industry as a viscosity improver or thickener to stabilize emulsions in various products wrapping ice cream. CMC is also a constituent of many non-food products such as personal lubricants, toothpastes, laxatives, diet pills, water-based paints, detergents, textile pastes, and various paper products. CMC is primarily used because it has a high viscosity, is non-toxic and is hypoallergenic.
例1−形態学的分析
本発明により提案する処理の後、繊維の構造を分析するために、形態学的分析走査型電子顕微鏡(SEM)を使用して行う。
Example 1-Morphological analysis After the treatment proposed by the present invention, a morphological analysis scanning electron microscope (SEM) is used to analyze the structure of the fibers.
CMCを基材とする市販のバインダー、市販の純粋なCMC、および本発明の方法から得たCMCをSEMにより比較する。 A commercial binder based on CMC, a commercially pure CMC, and a CMC obtained from the method of the present invention are compared by SEM.
SEMによる形態学的分析により、CMCを基材とする市販のバインダーが、Na2CO3を含むことがわかった(図1)。さらに、米国特許第4,948,430号は、その組成物中にNa2CO3を含むカルボキシメチルセルロースおよびそのようなバインダーの使用方法も記載している。しかし、市販の純粋なCMC中にはナトリウム塩は存在しない(図2)。 Morphological analysis by SEM showed that a commercially available binder based on CMC contains Na 2 CO 3 (FIG. 1). In addition, US Pat. No. 4,948,430 also describes carboxymethylcellulose containing Na 2 CO 3 in its composition and methods of using such binders. However, no sodium salt is present in commercially pure CMC (FIG. 2).
図3および図4は、本発明の方法から得られた生成物のSEM画像を示すものである。図3は、ココナツ繊維から得られた、漂白段階を経ていないCMCの顕微鏡写真を示し、図4は、ココナツ繊維から得た、漂白段階を経たCMCの画像を示し、得られた繊維構造が、市販の製品に見出される繊維と似ていることを立証している。 3 and 4 show SEM images of the product obtained from the method of the present invention. FIG. 3 shows a photomicrograph of CMC obtained from coconut fiber, which has not undergone the bleaching stage, and FIG. 4 shows an image of CMC obtained from coconut fiber, which has undergone the bleaching stage. It proves to be similar to the fibers found in commercial products.
例2−赤外分析
赤外分析(IR)の主目的は、エーテル化反応が実際にあったのか、それぞれの分子の振動に対応するバンドの特性を通して、確認することである。
Example 2-Infrared Analysis The main purpose of infrared analysis (IR) is to confirm whether the etherification reaction actually occurred through the characteristics of the bands corresponding to the vibrations of each molecule.
赤外分析は、漂白されたパルプ、ココナツ繊維から得られたCMC、市販の純粋なCMC、およびCMCを基剤とする市販のバインダーの各試料に行われた。 Infrared analysis was performed on each sample of bleached pulp, CMC obtained from coconut fibers, commercially pure CMC, and commercially available binders based on CMC.
漂白されたパルプのIR分析(図5)の目的は、セルロースの化学構造を確認することである。赤外スペクトルは、官能基O−H基(3500cm−1付近のバンド)およびアルキル基(2900cm−1付近のバンド)のバンドを示した。 The purpose of IR analysis (Figure 5) of the bleached pulp is to confirm the chemical structure of cellulose. The infrared spectrum showed bands of a functional group OH group (a band near 3500 cm −1 ) and an alkyl group (a band near 2900 cm −1 ).
ココナツ繊維(図6)および市販の純粋なCMC(図7)から得られたCMCスペクトルを比較することにより、我々は、カルボン酸ナトリウムのカルボニル基の軸方向変形の振動に対応する、1647〜1664cmcm−1における類似の振動数を有する、カルボニル(C−O)基の軸方向変形のピークにおける類似性を観察した。全ての赤外スペクトルは類似した特徴を示すが、ココナツ繊維から製造した試料におけるバンドの変位があり、そのような事実は、セルロースを得る際に、又はセルロースの分解により、他の化合物が生じたことにより説明される。 By comparing the CMC spectra obtained from coconut fiber (FIG. 6) and commercially available pure CMC (FIG. 7), we correspond to 1647-1664 cmcm corresponding to the vibration of the axial deformation of the carbonyl group of sodium carboxylate. Similarity was observed at the peak of axial deformation of the carbonyl (C—O) group with a similar frequency at −1 . All infrared spectra show similar characteristics, but there are band shifts in samples made from coconut fibers, such fact that other compounds were produced when obtaining cellulose or by degradation of cellulose Explained.
ココナツ繊維および市販の純粋なCMCおよびCMCを基剤とする市販のバインダーから得たCMC(図8)を比較することにより、赤外スペクトルに幾つかの違いを観察することができる。顕著な違いは、1770cm−1におけるバンドがより強く存在し、1660〜1640cm−1における吸収振動のバンドが存在しないことであり、そのようなバンドの変位は、ある量のNa2CO3がCMCに加わったことに起因し、前者は、さらに、より酸性の特徴をCMCに与えるので、カルボキシメチル基が、カルボン酸およびカルボキシラートエステルの形態で、より大きな量であることが表される。CMCを基剤とする市販のバインダーの赤外スペクトルに現れる、他のピークと異なった、もう一つのピークは、1448cm−1における強いピークの存在であり、これは、カーボナートカルボニル基のC−O変形によるものである。 By comparing CMC obtained from coconut fiber and commercially available pure CMC and a commercially available binder based on CMC (FIG. 8), several differences can be observed in the infrared spectrum. Significant difference is present stronger band at 1770 cm -1, is that there is no band absorption vibration at 1660~1640Cm -1, displacement of such band, the Na 2 CO 3 in an amount CMC The former further imparts more acidic characteristics to CMC, indicating that carboxymethyl groups are in greater amounts in the form of carboxylic acids and carboxylate esters. Another peak that appears in the infrared spectrum of a commercial binder based on CMC, unlike the other peaks, is the presence of a strong peak at 1448 cm −1 , which is the C— This is due to O deformation.
例3−ココナツ繊維から得たCMCを使用する鉄鉱石ペレット化
前に述べたように、本発明は、鉄鉱石粒子の凝集に有用であることが立証されている。この研究を補完するために、本発明の効果を立証するための試験を行った。
Example 3 Iron Ore Pelletization Using CMC Obtained from Coconut Fiber As previously stated, the present invention has proven useful for agglomeration of iron ore particles. To complement this study, tests were conducted to demonstrate the effectiveness of the present invention.
満足な結果が得られたペレット化と焼結ポットグレイトでのペレット化プラントの試験結果は図9に示した通りである。 The results of the pelletization and sintering pelletization plant test with satisfactory results were as shown in FIG.
試験は、表1に示すように、漂白段階を経た、および経ていない、CMCの使用を、CMCを基剤とする市販のバインダーと比較して行った。 The test was conducted as shown in Table 1 with the use of CMC, with and without a bleaching step, compared to a commercial binder based on CMC.
最後に、当然のことながらこれらの図等は、本発明の代表的な実施態様を示し、本発明の目的の実際の範囲は、請求項にのみ定義される。 Finally, it should be understood that these figures illustrate representative embodiments of the present invention, and the actual scope of the present invention is defined only by the claims.
Claims (14)
a)ココナツ繊維を含んでなる原料が、洗浄され、乾燥され、粉砕され、および再度洗浄される、原料を準備する工程、
b)工程a)から得られた生成物を混合し、水酸化ナトリウムと撹拌反応させ、その後、圧力と温度を加える、パルプ化工程、
c)工程b)から得られた生成物を漂白する、任意の漂白工程、
d)パルプを粉砕すること、イソプロパノールおよび蒸留水の溶液を室温で撹拌しながら加えること、NaOH水溶液を混合物がアルカリ化するまで加えること、イソプロパノール中のモノクロロ酢酸を加えること、濾過すること、メタノール溶液中に懸濁させること、および酢酸で中和させることからなる合成工程
を含んでなる、方法。 A method for obtaining carboxymethylcellulose from agricultural industrial residues, comprising the following steps:
a) preparing a raw material, wherein the raw material comprising coconut fiber is washed, dried, crushed and washed again;
b) mixing the product obtained from step a), reacting with sodium hydroxide with stirring, and then applying pressure and temperature, pulping step,
c) optional bleaching step of bleaching the product obtained from step b)
d) grinding the pulp, adding a solution of isopropanol and distilled water with stirring at room temperature, adding aqueous NaOH until the mixture is alkalized, adding monochloroacetic acid in isopropanol, filtering, methanol solution A process comprising a synthesis step consisting of suspending in and neutralizing with acetic acid.
そのカルボキシメチルセルロースを、炭酸ナトリウム、亜塩素酸ナトリウム、クエン酸ナトリウム、およびナトリウムグルコラートからなる群から選択される1種またはそれ以上の成分と混合することを含む、鉱石ペレット製造用バインダー組成物の製造方法。 Carboxymethylcellulose is produced by the method according to any one of claims 1 to 8,
A binder composition for producing ore pellets comprising mixing the carboxymethyl cellulose with one or more ingredients selected from the group consisting of sodium carbonate, sodium chlorite, sodium citrate, and sodium glucolate. Production method.
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US20130324711A1 (en) | 2013-12-05 |
TW201412776A (en) | 2014-04-01 |
EP2847232B1 (en) | 2018-09-12 |
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KR20150058099A (en) | 2015-05-28 |
BR112014028085A2 (en) | 2017-12-12 |
DK2847232T3 (en) | 2018-12-17 |
US9266968B2 (en) | 2016-02-23 |
AR091814A1 (en) | 2015-03-04 |
AU2013258896A1 (en) | 2015-01-22 |
SA113340539B1 (en) | 2016-03-27 |
WO2013166575A1 (en) | 2013-11-14 |
BR112014028085B1 (en) | 2021-04-13 |
AU2013258896B2 (en) | 2016-12-15 |
CN105143273A (en) | 2015-12-09 |
JP2015523418A (en) | 2015-08-13 |
EP2847232A1 (en) | 2015-03-18 |
PL2847232T3 (en) | 2019-05-31 |
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